CN114539754B - Weather-resistant halogen-free flame-retardant bio-based polycarbonate material and preparation method thereof - Google Patents
Weather-resistant halogen-free flame-retardant bio-based polycarbonate material and preparation method thereof Download PDFInfo
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- CN114539754B CN114539754B CN202111544316.3A CN202111544316A CN114539754B CN 114539754 B CN114539754 B CN 114539754B CN 202111544316 A CN202111544316 A CN 202111544316A CN 114539754 B CN114539754 B CN 114539754B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 125
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 114
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title description 23
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 47
- 229960002479 isosorbide Drugs 0.000 claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 claims abstract description 24
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 24
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 23
- 239000001205 polyphosphate Substances 0.000 claims abstract description 23
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical group O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 5
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 5
- NEFJPHDWZWTFQC-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;benzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 NEFJPHDWZWTFQC-UHFFFAOYSA-N 0.000 claims description 5
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 3
- 230000000052 comparative effect Effects 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000006081 fluorescent whitening agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000282866 Euchlaena mexicana Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- QLPZYYOHERFPKO-UHFFFAOYSA-N 1,2,3,4-tetrabromodibenzofuran Chemical compound C1=CC=C2C3=C(Br)C(Br)=C(Br)C(Br)=C3OC2=C1 QLPZYYOHERFPKO-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000013523 DOWSIL™ Substances 0.000 description 1
- 229920013731 Dowsil Polymers 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a weather-proof halogen-free flame-retardant bio-based polycarbonate material which is prepared from the following components in parts by weight: 50-70 parts of isosorbide type polycarbonate, 10-30 parts of arylate block copolycarbonate and SiO 2 1-10 parts of PC nano composite material, 1-10 parts of polyphosphate flame retardant, 1-4 parts of polyphenyl siloxane flame retardant, 1-5 parts of organosilicon toughening agent and 0.1-1 part of auxiliary agent. The flame retardant is compounded by the polyphosphate flame retardant and the polyphenyl siloxane flame retardant, is applied to the isosorbide type polycarbonate resin, has excellent comprehensive performance, and can meet the requirements of high heat resistance and high flame retardance.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a weather-resistant halogen-free flame-retardant bio-based polycarbonate material and a preparation method thereof.
Background
The polycarbonate is widely used in the technical fields of electronic appliances, automobiles, machine manufacturing, computers and the like because of the characteristics of heat resistance, flame retardance, good impact resistance, easiness in processing and molding, low cost and the like. However, from the viewpoint of environmental protection and sustainable development, since bisphenol a having biotoxicity needs to be used in the preparation process of polycarbonate, and part of the synthesis process involves phosgene and methylene dichloride which do not meet the environmental protection requirements, the research on environment-friendly bio-based polycarbonate is in the trend at the moment of increasing environmental protection awareness.
Isosorbide, which is considered as an important bio-based raw material next to lactic acid, is the only sugar alcohol monomer currently achieving industrial production. The isosorbide is used as the plastic raw material, so that the problem of environmental pollution of waste plastics can be effectively prevented. The characteristics of the isosorbide rigid molecule and chiral structure enable the isosorbide rigid molecule to be used as an important polymer monomer for constructing various polymers with high glass transition temperature and special properties. The bio-based polycarbonate prepared from isosorbide as a raw material has been industrialized as a high-quality engineering plastic and is used in the fields of optics, energy sources, electronic instruments and the like.
The isosorbide type polycarbonate has larger difference with the traditional bisphenol A type polycarbonate in terms of structure, has the characteristics of high transparency, good brightness and the like in terms of optical performance, has the characteristics of high surface hardness, high rigidity, tough surface, scratch resistance and the like in terms of physical and mechanical properties, but has greatly reduced temperature resistance, impact strength and flame retardance compared with the common bisphenol A polycarbonate; in addition, if the polymer chain segment is used outdoors for a long time, free radicals can be generated in the matrix under the action of illumination, and under the aerobic condition, the free radicals can induce the polymer chain segment oxidation reaction, so that the matrix is yellowing. In addition, although the scratch resistance of isosorbide type polycarbonate is significantly improved over bisphenol a polycarbonate, pencil hardness is also only F grade.
The polycarbonate resin composed of isosorbide is structurally different from known aromatic bisphenol a type aromatic polycarbonate resins. Thus, the combustion mechanism thereof is also different from that proposed for bisphenol a type aromatic polycarbonate resins, such as intramolecular transfer and isomerization to form a carbonized film. In addition, polycarbonate resins composed of isosorbide are also different from known bisphenol a type polycarbonate resins in terms of compatibility with flame retardants. Therefore, not all flame retardants used in aromatic polycarbonate resins can be used directly as in polycarbonate resins made of isosorbide, and thus a separate study is required.
The traditional brominated flame retardant has high flame retardant efficiency, but generates a large amount of smoke, tetrabromodibenzodioxane, tetrabromodibenzofuran and other cancerogenic substances in the combustion and thermal cracking processes; although the low-molecular phosphate flame retardant avoids harmful substances generated in the combustion process of a brominated flame retardant system, the low-molecular phosphate flame retardant has low melting point and high volatility, and is easy to cause great reduction of heat resistance of materials and volatilization loss in the forming process; the sulfonate flame retardant accelerates the carbonization rate of bisphenol A polycarbonate when burning, promotes the molecular crosslinking of the polymer, has small addition amount and high efficiency, can keep the material transparent, but can not meet the flame retardant requirement of thin-wall parts, and has poor flame retardant effect in isosorbide type polycarbonate; the phosphazene flame retardant has the advantages of excellent flame retardance, water resistance, oxidation resistance, thermal stability, molding processability, low smoke generation amount during combustion or thermal cracking, and the like, but has larger addition amount, and influences the heat resistance and the light transmittance of the material after the phosphazene flame retardant is added; the traditional polysiloxane flame retardant is important for researchers due to excellent processability, flame retardance and good mechanical properties, is particularly friendly to the environment, but has poor thin-wall flame retardant effect when being singly used, has large addition amount and high cost, and is generally used as a synergistic flame retardant for compounding. The phenyl organosiloxane flame retardant has better thermal stability, higher thermal decomposition activation energy and thermal decomposition temperature, and better flame retardant effect, and the higher the phenyl content of the silicon flame retardant, the denser the carbon layer formed after the prepared flame retardant material is combusted, and the better the flame retardant effect.
The patent application with publication number of CN 111548620A discloses an environment-friendly optical grade polycarbonate and a preparation method thereof, wherein the environment-friendly optical grade polycarbonate comprises 100 parts of isosorbide type polycarbonate, 0.1-0.4 part of antioxidant, 0.05 part of fluorescent whitening agent OB-1, 0.5-1.5 parts of light dispersing agent and 0.15 part of wetting agent; the preparation method comprises the following steps: taking isosorbide type polycarbonate, an antioxidant, a fluorescent whitening agent, liquid paraffin, an organosilicon light dispersing agent and an ultraviolet absorber, putting the mixture into a high-speed mixer, mixing for 5-10min at the speed of 900rpm to obtain a premix, and extruding, cooling, cutting and granulating by a double-screw extruder. The product of the invention can be used in the fields of lamp shades and the like, and has the advantages of high haze, good weather resistance and the like. The invention adopts the isosorbide type polycarbonate to add the light dispersing agent, improves the haze of the matrix, and adds the fluorescent whitening agent in the matrix to improve the whiteness of the matrix, and can absorb 270-280nm ultraviolet light due to the addition of the ultraviolet light absorbers UV-P and UV-329. The ultraviolet light absorbers UV-P and UV-329 are low molecular compounds, are easy to separate out in long-term outdoor use, and the fluorescent whitening agent is easy to change color in outdoor use. In addition, no improvement is made to the flame retardancy of the material.
Patent application publication No. CN113372705A discloses a transparent flame retardant polycarbonate, a preparation method thereof and a polycarbonate product. The transparent flame-retardant polycarbonate comprises the raw materials of polycarbonate, an ultraviolet absorber, an antioxidant A, a release agent and an ionic liquid flame-retardant master batch, wherein the ultraviolet absorber is used in an amount of 0.1-0.3 part, the antioxidant A is used in an amount of 0.2-0.6 part, the release agent is used in an amount of 0.3-0.6 part, and the ionic liquid flame-retardant master batch comprises 0.1-0.5 part of sulfonic acid functionalized ionic liquid based on 100 parts of polycarbonate by mass; the preparation method comprises the following steps: preparing flame-retardant master batches, weighing and stirring the raw materials according to the formula proportion for 5-10min, and extruding and granulating the mixed raw materials. The flame retardant system employed in this invention was found to be more suitable for polycarbonates of bisphenol a type structure, with poor results in isosorbide polycarbonate resins.
Patent application publication No. CN109749389A discloses a weather-resistant alloy material of isosorbide type polycarbonate and ABS resin and a preparation method thereof; the purpose is to provide a polycarbonate and ABS resin alloy which contains bio-based renewable components, is environment-friendly and has excellent heat resistance and weather resistance. The weather-resistant isosorbide type polycarbonate and ABS resin alloy material comprises the following components in parts by weight: 45-70% of isosorbide type polycarbonate, 30-50% of ABS resin, 5-10% of styrene-maleic anhydride copolymer SMA resin, 0.2-1% of antioxidant and 0.3-1% of ultraviolet light absorber. Also, the ultraviolet absorbers UV-234 and UV-328 are low molecular compounds, which are easily separated out during long-term outdoor use, and the fluorescent whitening agents are easily discolored during outdoor use. In addition, the problem of temperature resistance and flame retardance is not solved.
Patent application publication No. CN101679738A discloses a flame retardant polycarbonate resin polymer which is a resin composition containing a polycarbonate resin derived from an ether diol such as isosorbide and is excellent in flame retardancy, heat resistance, heat stability, rigidity, transparency and molding processability. The flame retardant adopts phosphorus-nitrogen flame retardant, and in a molded product with the thickness of 1.6mm, the UL94 flame retardant level is at least V2 grade, but the flame retardant effect is not good for a thin-wall product with the thickness of less than or equal to 1.2mm, and the weather-proof problem is not solved.
With the rapid development of science and technology, electronic components such as mobile phones, computers, televisions, air conditioners, power supplies, MP 3, MP4 and the like are increasingly thinned, and new requirements are put forward for flame retardant materials with protection functions on certain key parts. Therefore, it is very necessary to develop a bio-based polycarbonate material that is weather resistant, meets thin wall applications, is halogen free and flame retardant.
Disclosure of Invention
The invention aims to provide a weather-proof halogen-free flame-retardant bio-based polycarbonate material.
The invention also aims to provide a preparation method of the weather-resistant halogen-free flame-retardant bio-based polycarbonate material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a weather-resistant halogen-free flame-retardant bio-based polycarbonate material, which is prepared from the following components in parts by weight: 50-70 parts of isosorbide type polycarbonate, 10-30 parts of arylate block copolycarbonate and SiO 2 1-10 parts of PC nano composite material, 1-10 parts of polyphosphate flame retardant, 1-4 parts of polyphenyl siloxane flame retardant, 1-5 parts of organosilicon toughening agent and 0.1-1 part of auxiliary agent.
The weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 55-65 parts of isosorbide type polycarbonate, 15-25 parts of arylate block copolycarbonate and SiO 2 2-10 parts of PC nano composite material, 2-10 parts of polyphosphate flame retardant, 2-4 parts of polyphenyl siloxane flame retardant, 2-5 parts of organosilicon toughening agent and 0.2-1 part of auxiliary agent.
The weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 55-65 parts of isosorbide type polycarbonate, 15-25 parts of arylate block copolycarbonate and SiO 2 4-10 parts of PC nano composite material, 4-10 parts of polyphosphate flame retardant, 3-4 parts of polyphenyl siloxane flame retardant, 3-5 parts of organosilicon toughening agent and 0.5-0.9 part of auxiliary agent.
The weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 62.2 parts of isosorbide type polycarbonate, 20 parts of arylate block copolycarbonate and SiO 2 5 parts of PC nano composite material, 6 parts of polyphosphate flame retardant, 3 parts of polyphenyl siloxane flame retardant, 3 parts of organosilicon toughening agent and 0.8 part of auxiliary agent.
The isosorbide type polycarbonate is a polycarbonate resin obtained by copolymerizing isosorbide and diphenyl carbonate, and the relative molecular weight of the isosorbide type polycarbonate is 20000-30000; a specific alternative is the product available from Mitsubishi corporation under the model DURABIO D7340, which comprises a polymer having the formula:
wherein R is selected from the group consisting of C1-C10 alkylene, C6-C18 arylene, alkoxylated C1-C10 alkylene, preferably phenylene; m and n are each selected from 1 to 1000 (preferably 100).
The relative molecular weight of the arylate segmented carbonate is 20000-30000, wherein the carbonate block consists of bisphenol A carbonate units, and the arylate block is resorcinol isophthalate block, and the product with the model of SLX 2432T provided by SABIC company can be selected.
The SiO is 2 The preparation method of the PC nano composite material comprises the following steps: preparation of SiO by sol-gel method using Polycarbonate (PC) as matrix and Tetraethoxysilane (TEOS) as inorganic disperse phase 2 PC nanocomposite.
The SiO is 2 The particle size of the PC nano composite material is 20-60 nm, and the specific preparation method comprises the following steps: weighing 5g of PC, magnetically stirring until the PC is completely dissolved in 30ml of tetrahydrofuran under the condition of heating and refluxing, adding 0.8g of TEOS into the solution, and magnetically stirring for 10min; then adding 0.975g of acetone, and mixing to obtain a homogeneous solution; then 0.3g of pH 2.0 is slowly addedThe mixed solution of water and hydrochloric acid (dropwise adding, controlling hydrolysis speed), refluxing and stirring for 2 hours, curing gel, removing solvent, and oven drying at 120deg.C for 2 hours to obtain SiO 2 PC nanocomposite. Wherein, the PC is bisphenol A type aromatic polycarbonate resin 2805, tetrahydrofuran, tetraethoxysilane, acetone, hydrochloric acid and deionized water which are commercially available (specific reference document: chen Chunhua. Preparation and performance study of polycarbonate nanocomposite, university of Tai-Ji-Job, 2008, 18-25.).
The relative molecular weight of the polyphosphate flame retardant is 40000-50000, and the model is HM1100 manufactured by FRX Polymers company of America.
The polyphenyl siloxane flame retardant is octaphenyl cyclotetrasiloxane, and the molecular structure is as follows:
the preparation method of the octaphenyl cyclotetrasiloxane comprises the following steps: 200g of diphenyl dimethoxy silane, 320g of acetone and 8g of deionized water are put into a three-port bottle provided with a stirring device, a condenser and a thermometer, the three-port bottle is fully stirred to be uniformly mixed, 0.05g of NaOH is dissolved in a beaker containing 20g of methanol, the three-port bottle is put into the three-port bottle after being uniformly mixed, the temperature is raised to 55 ℃, the reflux is started, the reaction is carried out for 4 hours, the three-port bottle is subjected to suction filtration after the reaction is finished, the three-port bottle is washed with absolute ethyl alcohol for 3 times, the three-port bottle is washed with deionized water until filtrate is neutral, and the eight-phenyl cyclotetrasiloxane in a white crystal shape is obtained after vacuum drying. Wherein diphenyldimethoxysilane, acetone, sodium hydroxide and methanol are used commercially (specific references: yang Rui, etc., research on a high-phenyl-content silicone flame-retardant polycarbonate, engineering science and technology, 2021, 195-202.)
The organosilicon toughening agent is a core-shell graft copolymer with a core of silicon rubber-acrylic ester and a shell of polymethyl methacrylate, and the silicon content is 70-80%, and the organosilicon toughening agent is selected from Mitsubishi positive company of Japan, and the model is SX-005.
The auxiliary agent is prepared from an antioxidant, a processing auxiliary agent and toner in a mass ratio of 4:3:1.
The antioxidant is at least one of phosphite antioxidant 168, S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076, preferably the mixture of antioxidant S-9228 and antioxidant 1076. Antioxidant S-9228 is manufactured by the company Dover and antioxidant 1076 is manufactured by the company BASF.
The processing aid is at least one of polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate and long-chain fatty acid multifunctional ester, and preferably pentaerythritol stearate. Polyethylene wax, oxidized polyethylene wax, and pentaerythritol stearate were manufactured by BASF corporation, and long chain fatty acid multifunctional esters were manufactured by sonsha corporation, germany.
The toner consists of pigment and lubricant, wherein the pigment is phthalocyanine blue, phthalocyanine green, BR red, HG yellow, 3R blue and the like, and can be purchased from Coryn chemical industry (China) limited company; the lubricant is EBS, and the mass ratio of pigment phthalocyanine blue to lubricant EBS is 1: 10.
The invention provides a preparation method of the weather-resistant halogen-free flame-retardant bio-based polycarbonate material, which comprises the following steps:
firstly, drying isosorbide type polycarbonate for 6 hours at the temperature of 100 ℃ of a blast dryer, drying arylate segmented carbonate for 6 hours at the temperature of 120 ℃ of the blast dryer, and drying a polyphosphate flame retardant for 6 hours in a vacuum oven at the temperature of 100 ℃; then the dried isosorbide type polycarbonate, the dried arylate block copolycarbonate and SiO 2 Fully mixing the PC nanocomposite, the dried polyphosphate flame retardant, the polyphenyl siloxane flame retardant, the organosilicon toughening agent and the auxiliary agent in a high-speed mixer for 6-8 minutes, uniformly mixing, and then feeding the mixture into a double-screw extruder for melt blending and granulating;
the temperature of the 11 region of the twin-screw extruder was set at 220 ℃, 240 ℃, 260 ℃ respectively 260 ℃, 250 ℃ and 250 DEG C250 ℃, 250 ℃;
the obtained granules are dried for 4 hours at 100 ℃, and are injection molded into standard sample bars at 250-270 ℃ to obtain the weather-proof halogen-free flame-retardant bio-based polycarbonate material.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
the flame retardant is compounded by the polyphosphate flame retardant and the polyphenyl siloxane flame retardant, is applied to the isosorbide type polycarbonate resin, has excellent comprehensive performance, and can meet the requirements of high heat resistance and high flame retardance.
According to the invention, due to the introduction of the arylation block copolycarbonate, the material has excellent weather resistance on the premise of no addition of an ultraviolet additive, and can meet the outdoor use requirement.
In the invention, due to SiO 2 The addition of the PC nano composite material not only improves the heat resistance and scratch resistance of the material, but also further improves the weather resistance of the material, and plays a role in flame retardant synergy.
The addition of the toughening agent with high silicon content not only improves the shock resistance of the material, but also is beneficial to improving the flame retardant property.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The silsesquioxane flame retardants used in the following comparative examples of the present invention: manufactured by Dow Corning Co., ltd., model DOWSIL TM 40-001; branched polysiloxane flame retardant: manufactured by the american type of doucorning company, model FAC-107.
The isosorbide type polycarbonate used in the embodiment of the invention is a polycarbonate resin obtained by copolymerizing isosorbide and diphenyl carbonate, and the relative molecular weight of the isosorbide type polycarbonate resin is 20000-30000; a specific alternative is the product available from Mitsubishi corporation under the model DURABIO D7340, which comprises a polymer having the formula:
wherein R is selected from the group consisting of C1-C10 alkylene, C6-C18 arylene, alkoxylated C1-C10 alkylene, preferably phenylene; m and n are each selected from 1 to 1000 (preferably 100).
The arylate block copolycarbonate used in the examples of the present invention has a relative molecular weight of 20000 to 30000, wherein the carbonate block is composed of bisphenol a carbonate units, and the arylate block is resorcinol isophthalate block, and specifically, the product of the company SABIC under the model SLX 2432T may be selected.
SiO used in the examples of the present invention 2 The preparation method of the PC nano composite material comprises the following steps: preparation of SiO by sol-gel method using Polycarbonate (PC) as matrix and Tetraethoxysilane (TEOS) as inorganic disperse phase 2 PC nanocomposite.
The SiO is 2 The particle size of the PC nano composite material is 20-60 nm, and the specific preparation method comprises the following steps: weighing 5g of PC, magnetically stirring until the PC is completely dissolved in 30ml of tetrahydrofuran under the condition of heating and refluxing, adding 0.8g of TEOS into the solution, and magnetically stirring for 10min; then adding 0.975g of acetone, and mixing to obtain a homogeneous solution; slowly adding 0.3g of mixed solution of water and hydrochloric acid with pH value of 2.0 (dropwise adding, controlling hydrolysis speed), refluxing and stirring for 2 hr, aging gel, removing solvent, and oven drying at 120deg.C for 2 hr to obtain SiO 2 PC nanocomposite. Wherein, the PC is bisphenol A type aromatic polycarbonate resin 2805, tetrahydrofuran, tetraethoxysilane, acetone, hydrochloric acid and deionized water which are commercially available (specific reference document: chen Chunhua. Preparation and performance study of polycarbonate nanocomposite, university of Tai-Ji-Job, 2008, 18-25.).
The relative molecular weight of the polyphosphate flame retardant used in the embodiment of the invention is 40000-50000, and the model is HM1100 manufactured by FRX Polymers company of America.
The polyphenyl siloxane flame retardant used in the embodiment of the invention is octaphenyl cyclotetrasiloxane, and the molecular structure is as follows:
the preparation method of the octaphenyl cyclotetrasiloxane comprises the following steps: 200g of diphenyl dimethoxy silane, 320g of acetone and 8g of deionized water are put into a three-port bottle provided with a stirring device, a condenser and a thermometer, the three-port bottle is fully stirred to be uniformly mixed, 0.05g of NaOH is dissolved in a beaker containing 20g of methanol, the three-port bottle is put into the three-port bottle after being uniformly mixed, the temperature is raised to 55 ℃, the reflux is started, the reaction is carried out for 4 hours, the three-port bottle is subjected to suction filtration after the reaction is finished, the three-port bottle is washed with absolute ethyl alcohol for 3 times, the three-port bottle is washed with deionized water until filtrate is neutral, and the eight-phenyl cyclotetrasiloxane in a white crystal shape is obtained after vacuum drying. Wherein diphenyldimethoxysilane, acetone, sodium hydroxide and methanol are used commercially (specific references: yang Rui, etc., research on a high-phenyl-content silicone flame-retardant polycarbonate, engineering science and technology, 2021, 195-202.)
The organic silicon toughening agent used in the embodiment of the invention is a core-shell structure graft copolymer with silicone rubber-acrylic ester as a core and polymethyl methacrylate as a shell, and the silicon content is 70-80%, and the model is SX-005, which is selected from Mitsubishi positive company of Japan.
The auxiliary agent used in the embodiment of the invention is prepared from an antioxidant, a processing auxiliary agent and toner in a mass ratio of 4:3:1. The antioxidant is a mixture of antioxidant S-9228 and antioxidant 1076, the processing aid is pentaerythritol stearate, the toner is composed of pigment and lubricant EBS, and the mass ratio of pigment phthalocyanine blue to lubricant EBS is 1: 10.
The inventive examples 1-5 and comparative examples 1-7, 9 were prepared according to the following preparation method, comprising the following steps:
firstly, drying isosorbide type polycarbonate for 6 hours at the temperature of 100 ℃ of a blast dryer, drying arylate segmented carbonate for 6 hours at the temperature of 120 ℃ of the blast dryer, and drying a polyphosphate flame retardant for 6 hours in a vacuum oven at the temperature of 100 ℃; then isosorbide type polycarbonate, arylated block copolycarbonate and SiO 2 PC nano composite material, polyphosphate flame retardant, polyphenyl siloxane flame retardant, organosilicon toughening agent and auxiliary agent are mixed at high speedFully mixing for 6-8 minutes in a machine, uniformly mixing, and then feeding the mixture into a double-screw extruder for melt blending and granulating;
the temperature of the 11 region of the twin-screw extruder was set at 220 ℃, 240 ℃, 260 ℃ respectively 260 ℃, 250 ℃ and 250 DEG C250 ℃, 250 ℃;
the obtained granules are dried for 4 hours at 100 ℃, and are injection molded into standard sample bars at 250-270 ℃ to obtain the weather-proof halogen-free flame-retardant bio-based polycarbonate material.
Tables 1 and 2 show the formulation proportions of inventive examples 1 to 5 and comparative examples 1 to 9 and DURABIO D7340 alone as a comparison:
TABLE 1 comparative examples 1-3 and examples 1-5 Components and proportions
Table 2 Components and proportions of comparative examples 4 to 9
Preparation method of comparative example 8: firstly, drying isosorbide type polycarbonate for 6 hours at the temperature of 100 ℃ of a blast dryer, drying arylate segmented copolycarbonate for 6 hours at the temperature of 120 ℃ of the blast dryer, drying a polyphosphate flame retardant for 6 hours in a vacuum oven at the temperature of 100 ℃, and heating a silsesquioxane flame retardant for 4 hours at the temperature of 80 ℃ for later use; and then fully mixing the raw materials in a high-speed mixer for 6-8 minutes, uniformly mixing, feeding the mixture into a double-screw extruder through a main feeder, performing melt blending granulation, and injecting the silsesquioxane flame retardant through a lateral feeding hole by a liquid metering pump.
The temperature in zone 11 of the twin-screw extruder was set at 240℃at 250℃at 260℃at 250℃at 240℃at 250 ℃. The obtained granules are dried for 4 hours at 100 ℃, and are injection molded into standard sample bars at 250-270 ℃ to obtain the finished product.
Evaluation of implementation Effect
The samples obtained in examples 1 to 5 and comparative examples 1 to 9 above were tested for mechanical properties according to the American Society for Testing and Materials (ASTM) standard, for flame retardant properties according to the UL94 standard, for surface hardness of materials according to the GB/T6739 standard using pencil method, for flame retardancy according to the UL94 standard, for weather resistance (15 cycles) according to the GB/T2423-2013 program B, and for color change grey scale according to ISO 105-A02. The test results are shown in tables 3 and 4:
TABLE 3 test results for comparative examples 1-3 and examples 1-5
Table 4 test results for comparative examples 4-9
The test performance results of tables 3 and 4 show that:
comparative examples 1-5 found that the combination of polyphosphate flame retardant and polyphenyl siloxane flame retardant is applied to isosorbide type polycarbonate resin, has excellent comprehensive performance and can meet the requirements of high heat resistance and high flame retardance. Comparison of comparative examples 1, 2 and 9 shows that the flame retardant effect is poor and the thin-wall flame retardant requirement cannot be satisfied when the polyphosphate flame retardant is used alone or the polyphenylsiloxane flame retardant is used alone in the isosorbide type polycarbonate resin. From comparative example 5, it was found that: in the isosorbide type polycarbonate resin, the polyphosphate flame retardant alone is used, and even if the addition amount reaches 12%, the flame retardant effect is still poor.
Comparative example 1, example 2 and comparative example 3 found that SiO 2 The addition of the PC nano composite material not only improves the heat resistance and scratch resistance of the material, but also further improves the weather resistance of the material, and plays a role in flame retardant synergy. However, with increasing amounts of addition, the impact properties of the material are significantly reduced. The optimum formulation should therefore be example 1.
Comparative example 1, comparative example 8 and comparative example 9 have found that the molecular chain of the silicon-based flame retardant is Si-O bond, the bond energy is high, the thermal stability is excellent, the organic silicon can promote the generation of a carbon layer during combustion, the formation of smoke and the development of flame are prevented, and the flame retardant effect is improved. The phenyl organosilicon flame retardant has better flame retardant effect due to higher thermal decomposition activation energy and thermal decomposition temperature; and the higher the phenyl content is, the more compact the carbon layer is formed after combustion, and the better the flame retardant effect is.
Comparative example 1, comparative example 1 and comparative example 6 find that the arylate block copolycarbonate was introduced in example 1, and the arylate block was a resorcinol isophthalate block. Resorcinol isophthalate exposure to uv radiation can cause a rapid photochemically induced rearrangement (photo-fries rearrangement) to form 2-hydroxybenzophenones at the surface which act as uv absorbers and stabilizers for the polymer. On the premise of no addition of ultraviolet additives, the material has excellent weather resistance and can meet the requirement of outdoor use. Comparative example 1 and comparative example 7 found that as the content of arylated block copolycarbonate increased, the surface hardness of the material decreased significantly, so that the optimum compounding ratio was to be example 1.
Comparative example 1, example 5 and comparative example 4 found that: the toughening agent with high silicon content is added, so that the impact resistance of the material is improved, and the flame retardant property is improved; however, as the amount of the additive increases, the heat resistance and surface hardness of the material decrease, and thus the optimum blending ratio should be example 1.
Comparative example 10
The patent application with publication number of CN107163537A discloses an antistatic scratch-resistant flame-retardant polycarbonate composite material which comprises the following components in parts by weight: 200-400 parts of siloxane copolymerized PC resin, 335-760 parts of DMBPC-PC copolymer, 5-50 parts of organosilicon toughening agent, 10-100 parts of nano scratch-proof composite material, 10-50 parts of flame retardant, 10-50 parts of antistatic agent and 5-15 parts of auxiliary agent. According to the invention, the siloxane copolymerized PC, the DMBPC-PC copolymer and the nano scratch-proof composite material are used in a composite manner, so that the scratch resistance of the surface of a product is obviously improved, and the surface hardness can be improved to 2H; the siloxane copolymerization PC and the organosilicon toughening agent ensure good mechanical properties of the material, especially normal-temperature and low-temperature impact properties. The composite resin has obvious antistatic effect, ensures certain transparency, has light transmittance reaching 76 percent and flame retardance reaching V-0 level.
Although the nanometer scratch-proof composite material is applied to siloxane copolypc and DMBPC-PC copolymer in the document, the scratch resistance of the surface of the product is obviously improved, and the surface hardness can be improved to 2H. However, the flame retardant adopted is brominated polycarbonate, and the molecular structure is as follows:
as the bromine content is up to 58%, the flame retardant efficiency of the brominated polycarbonate is high, but a large amount of smoke, corrosive gas and toxic gas are generated in the combustion and thermal cracking processes, and the brominated polycarbonate does not meet the environmental protection requirement.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. Weather-resistant halogen-free flame-retardant bio-based polycarbonate materialThe composite material is characterized by being prepared from the following components in parts by weight: 50-70 parts of isosorbide type polycarbonate, 10-30 parts of arylate block copolycarbonate and SiO 2 1-10 parts of PC nano composite material, 1-10 parts of polyphosphate flame retardant, 1-4 parts of polyphenyl siloxane flame retardant, 1-5 parts of organosilicon toughening agent and 0.1-1 part of auxiliary agent;
the auxiliary agent is prepared from an antioxidant, a processing auxiliary agent and toner in a mass ratio of 4:3:1.
2. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 1, wherein the weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 55-65 parts of isosorbide type polycarbonate, 15-25 parts of arylate block copolycarbonate and SiO 2 2-10 parts of PC nano composite material, 2-10 parts of polyphosphate flame retardant, 2-4 parts of polyphenyl siloxane flame retardant, 2-5 parts of organosilicon toughening agent and 0.2-1 part of auxiliary agent.
3. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 2, wherein the weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 55-65 parts of isosorbide type polycarbonate, 15-25 parts of arylate block copolycarbonate and SiO 2 4-10 parts of PC nano composite material, 4-10 parts of polyphosphate flame retardant, 3-4 parts of polyphenyl siloxane flame retardant, 3-5 parts of organosilicon toughening agent and 0.5-0.9 part of auxiliary agent.
4. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 3, wherein the weather-resistant halogen-free flame-retardant bio-based polycarbonate material is prepared from the following components in parts by weight: 62.2 parts of isosorbide type polycarbonate, 20 parts of arylate block copolycarbonate and SiO 2 5 parts of PC nano composite material, 6 parts of polyphosphate flame retardant, 3 parts of polyphenyl siloxane flame retardant, 3 parts of organosilicon toughening agent and 0.8 part of auxiliary agent.
5. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 1, wherein the isosorbide type polycarbonate is a polycarbonate resin obtained by copolymerizing isosorbide and diphenyl carbonate, and the relative molecular weight thereof is 20000 to 30000.
6. The weatherable halogen-free flame retardant bio-based polycarbonate material according to claim 1, wherein the arylate block copolycarbonate has a relative molecular weight of 20000 to 30000, wherein the carbonate blocks consist of bisphenol a carbonate units and the arylate blocks are resorcinol isophthalate blocks.
7. The weatherable halogen-free flame retardant bio-based polycarbonate material according to claim 1, wherein the relative molecular weight of the polyphosphate flame retardant is 40000-50000;
the polyphenyl siloxane flame retardant is octaphenyl cyclotetrasiloxane.
8. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 1, wherein the organosilicon toughening agent is a core-shell graft copolymer with a silicone rubber-acrylic ester as a core and polymethyl methacrylate as a shell, and the silicon content is 70-80%;
the processing aid is at least one of polyethylene wax, oxidized polyethylene wax and pentaerythritol stearate.
9. The weather-resistant halogen-free flame-retardant bio-based polycarbonate material according to claim 1, wherein the toner is composed of pigment and lubricant, wherein the pigment is selected from the group consisting of phthalocyanine blue, phthalocyanine green, BR red, HG yellow and 3R blue, the lubricant is EBS, and the mass ratio of the pigment to the lubricant is 1: 10.
10. A method for preparing the weather-resistant halogen-free flame retardant bio-based polycarbonate material according to any one of claims 1 to 9, comprising the steps of:
drying isosorbide type polycarbonate, dried arylate block copolycarbonate and SiO 2 Fully mixing the PC nanocomposite, the dried polyphosphate flame retardant, the polyphenyl siloxane flame retardant, the organosilicon toughening agent and the auxiliary agent in a high-speed mixer for 6-8 minutes, uniformly mixing, and then feeding the mixture into a double-screw extruder for melt blending and granulating;
the temperature of the 11 region of the twin-screw extruder was set at 220 ℃, 240 ℃, 260 ℃ respectively 260 ℃, 250 ℃ and 250 DEG C250 ℃, 250 ℃;
the obtained granules are dried for 4 hours at 100 ℃, and are injection molded into standard sample bars at 250-270 ℃ to obtain the weather-proof halogen-free flame-retardant bio-based polycarbonate material.
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